Oil soluble butenylphenol formaldehyde resins



United States Patent OIL SOLUBLE BUTENYLPHENOL;

FORMALDEHY DE RESINS Roger M. Christensen, Whitefish Bay, and Lowell 0. Cummings, Milwaukee, Wis., assignors to Pittsburgh Plate Glass Company No Drawing. Application May'3, 1954 Serial No. 427,385

7 Claims. (-cl; 260-19) This invention relates to novel varnish compositions, and pertains more particularly to oleoresinous type varnishes, the resinous component of which is a phenolic resin obtained by the condensation of a mixture of alkenylphenols with an aldehyde.

Among the synthetic resins used as ingredients of varnishes and related coating compositions are those of the a1kyl-phenol-formaldehyde, alkyd, maleic, urea-formaldehyde, coumarone-indene, acrylic, vinyl, and polystyrene type. The alkylphenol-formaldehyde resins are important from the commercial standpoint. phenol-aldehyde resins, however, possess certain disadvantages; for example, they produce slow bodying and drying varnishes with most drying oils including linseed oil and soybean oil. a fast bodying and drying varnish utilizing an alkylphenol-formaldehyde resin, it is necessary to employ as the drying oil component thereof, special drying oils such as tung oil, which is much more expensive than linseed or soybean oil and which is not always available in quantities sufficient to meet the needs therefor.

It is known that resins prepared by the condensation of an alkenylphenol, such as o-crotylphenol, with formaldehyde, are compatible with drying oils and can be used to form coating compositions. However, the resins obtained in this manner tend to be an undesirable red in color and consequently find but little application as varnish resins. Such resins also produce slow drying films, requiring several hours of heating at 125 C. to 150 C.

In copending applications, Serial Nos. 390,088 and 390,089, both filed November 3, 1953, it is disclosed that light colored, fast curing resins can be obtained by condensing a mixture of alkenylphenols, ordinarily including mono-, diand trialkenylphenols, with an alde: hyde, particularly formaldehyde.

It has now been discovered that the light colored resins obtained by condensing mixtures of alkenylphenols with an aldehyde are very compatible with drying oils and semi-drying oils, and give fast bodying and drying compositions, even when economical drying oils such as linseed oil and soybean oil are utilized as the oil compo nent of the varnish composition. Thus, by utilizing resins of the type dislosed in the copending applications referred to hereinabove, it is possible to obtainlight colored, fast bodying and fast drying varnish compositions utilizing inexpensive drying oils, a combination of useful properties which it has not been possible to obtain from phenol-aldehyde resins employed heretofore. Moreover,

Even the alkyl- Consequently, in order to obtain the hardness, impact resistance, mar resistance, flexibility and toughness of the resulting varnish compositions are entirely satisfactory for most applications.

The mixture of alkenylphenols which is condensed with an aldehyde to give the resins utilized in preparing the varnish compositions of the present invention may vary widely in composition. Ordinarily, the predominant component of the mixture is one or more monoalkenylphenols (including ortho,-- and para-monoalkenylphenols), the monoalkenyl component constituting about 55 percent to 85 percent by weight of the total mixture. The balance of the mixture (about 15 percent to 45 percent) is composed primarily of diand trialkenylphenols, although other phenolic materials, including polyphenols such as alkane diandtriphenols may also be present, depending upon the method by which the alkenylphenol mixture is prepared.

Mixtures of alkenylphenols of the type described in the foregoing paragraph are readily obtained by the methods'described in copending applications, Serial No. 300,- 359, filed July 22, 1952, and Serial Nos. 337,226, 337,- 227, 337,228 and 337,229, all filed February 16, 1953, the latter two applications are now abandoned. The methods described in these copending applications involve the reaction of conjugated dienes with phenolic compounds in the presence of certain catalysts such as the Friedel- Craftscompounds. For example, the product obtained by the reaction of butadiene-1,3 and phenol in the presence of an aqueous sulfuric acid catalyst is generally composed of less than about 15 percent unreacted phenol, less than about 5 percent of ethers, 55 to percent of monobutenylphenols and 15 to 50 percent of the higher boilingphenols including diand tributenylphenols and polyphenols. Ordinarily, the unreacted phenol and ethers will be removed from the reaction mixture by distillation before the condensation reaction with an aldehyde is carried out; however, this is not a critical expedient and the condensation reaction takes place readily even though theiunreact'ed phenols and ethers are not removed. Mixtures containing smaller quantities of monoalkenylphenols and larger quantities of the higher boiling phenols, for example, about 50 percent monoalkenylphenols and 30 to 50 percent of higher boiling phenols and the balance polyphenols and ethers, may also be employed with good results, as may mixtures containing no monoalkenylphenols. Also, the mixture may be composed entirely of ortho: and para-monoalkenylphenols, and in fact, ex cellent resins are obtained when such a mixture is employed. Mixtures of alkenylphenols with minor amounts of other phenols containing no unsaturated side chain, such as phenol, butylphenol, amylphenol and the like may also be used.

It is to be understood that mixtures of alkenylphenols can also be obtained by other methods known to the art addition to the reaction of conjugated dienes with phenolic compounds, and it is intended that the present invention include the use of any mixture of alkenylphenols regardless of the method whereby it is obtained.

Asillustrative of the alkenyl substituted phenolic compounds-whichin admixture are condensed with an aldehyde to form the novel resins of the present invention there are set forth below the products of the reaction of gam 3, n P astic];

- -cn -on;on-on:

A mixture of the above alkenylphenols forms excellent resins when condensed with an aldehyde in the presence of an alkaline catalyst. r

In general, the alkenylphenolic compounds in the mixtures condensed with aldehydes possess the structure R is alkenyl, cycl'oalkenyl, haloalkenyl, halocycloalkenyl, alkoxyalkenyl or alkoxycycloalkenyl and n and n; are whole'numbers, ordinarily from 1 to 3.

applications.

The preferred alkenylphenolic compounds for condensation with aldehydes in accordance with the present invention are mixtures of the butenylphenols, including orthoand para-Z-butenylphenols, di-2-butenylphen0ls and tri-2-butenylphenols. However, mixtures of other alkenylphenolic compounds may also be used, including butenylcresols, butenylcatechols, butenyl-2,3-dimethoxyphenols, mono-, diand tributenylresorcinol, mono-, di-

and tributenylguaiacol, 2-chlorobutenylcresol, 2-chlorohutenylphenol, 2-iodobutenylphenol, orthoand para-cy-' clopentenylphenol, pentenylphenol, pentenylcresol, pen tenylguaiacol, halopentenylphcnols, halo'pentenylguaia-v cols, and the like. I i

It may he that the trialkenyipheuols such as the tributenylphenols do not actually 'condense withaldehydes as do the monoand dialkenylphenols, but instead react through the unsaturated linkages and the OH group. Thistype of reaction is, of course, not possible withconventional phenols and may account for the improved bodying and drying rates possessed by varnishes prepared utilizing as the resinous component the condensation product of a mixture of alkenylphenols with an aldehyde.

Any aldehyde may be utilized in the preparation of the resins of the present invention. containing only atoms of carbon, hydrogen and oxygen, and particularly formaldehyde, are greatly preferred. In place of formaldehyde, a material which decomposes upon heating to yield formaldehyde, for example paraformaldehyde or trioxymethylene, may be utilized in the condensation reaction. An aqueous 37 percent formaldehyde solution is generally used very successfully.

In carrying out the condensation ,of a mixture of alkenylphenols with an aldehyde either an alkaline or acid catalyst is employed. Suitable alkaline materials,

Preferably, the sum of n and n is from 2 m4. Thealkenyl compounds of the above structure are all readily obtained by there. action of phenolic compounds with conjugated dienes in. accordance with the methods described in the copending However, aldehydes include sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, ammonia, hexamethylenetetramine and the like. Acidic materials which may be used include mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and organic carboxylic acids such as acetic acid, propionic acid, oxalic acid, and the like.

The quantity of catalyst utilized may be varied considerably. For example, when an alkaline catalyst is employed, it is generally desirable that about one-fourth equivalent of catalyst be present for each equivalent of alkenylphenolic compounds. Based upon the total weight of the reactants, about 0.5 percent to about 5.0 percent of the alkaline catalyst is used. When an acidic material is employed to catalyze the condensation reaction, it is also desirable that about 0.5 percent to about 5.0 percent, based upon the total weight of the reactants, be employed. Larger amounts of the catalyst may be utilized if desired.

Alternatively, the catalyst may be dispensed with entirely, although higher reaction temperatures may then be required with attendant increase in darkening of the resinous product.

The molar ratio of aldehyde to alkcnylphenols utilized in carrying out the condensation reaction may be varied Widely, and depends somewhat on whether an acidic or alkaline catalyst is used. When an alkaline catalyst is used, best results are, obtained when about 2.0 moles of the aldehyde are utilized for each mole of the alkenylphenolic compounds in the reaction mixture. However, the ratio may be as low or lower than 0.5 to 1.0 or as as high or higher than 5.0 to 1.0. When the ratio is much below the preferred 1.5 to 2.0 ratio the resinous product tends to belhard and more difiiculnyproeessabie. When the ratio is substantially above 1.5, to 1.0 good results are obtainedfbut, there is no economical'advantage in utilizing such'large excess of the aldehyde.

On-the-otherhand, when an acidc'atalyst is used, most useful resins are obtained when, less than a mole of the aldehydeis employed for each mole oi the alkenylphenolic component in the reaction mixture, with about 0.8 mole of aldehyde to 1.0 mole of the mixtureof alkenylphenolic compounds apparently being the optimum. However, the ratio may be as low or lower than 0.5 to 1.0 or as high orhigher than 5.0 to 1.0. Whenthe ratio is substantially above 1.5 to 1.0 no advantage is obtained. and infact, gels, rather than hardresins, maybe formed. Consequently, the use of such an uneconomical excess is not particularly desirable.

The alkaline condensation reactionv is best carried out by first admixing the alkenylphenols and the catalyst under an inert atmosphere such as nitrogen, and/or in thepresence of sodium hydrosulfitc, utilizing'suiticient' cooling to maintain the resulting reaction mixture at about room temperature-(25 (1.). When soluticn'isobtained the aldehyde is added at a moderate rate and cooling is applied as neededto keep the temperature below about 35 C. Care should betaken to keep-traces of air out of the.,reactor at all times during the condensation. Stirring is continued for about 48 hours at room temperature.

Atthe endv of this time the reaction mixture is care fully acidified to a pH of about 5.0 with a mineral acid such as hydrochloric acid or sulfuric acid, 01' a carboxylic acid such as acetic acid or propion-ic acid. Two layers are formed, a water layer and an alkenylphenolic resin layer, The Water layer is drawn oh and the water-in soluble layer .of resin is water washed 4 0rd times. At.

hydrated by vacuum'stripping at steam temperatures and ata pressure of about-20mm. "to'SS'rnm: Alternatively,

the Water can be removed by adding butanol and then carrying out an azeotropic distillation.

While the above describe-l method for carrying out the condensation is preferred, particularly when the alkenylphenol mixture is amixture of butenylphenols, other methods of carrying out the condensation, for example, simply by admixing the reactants and catalyst and allowing the mixture to stand at room temperature for about 48 hours, or by maintaining the reaction mixture at temperatures as high as 100 C. or higher, may also be utilized. In the event that higher temperatures are utilized the condensation will, of course, require less time than when the condensation is carried out at room temperature.

While the resins obtained by the alkaline condensation of a mixture of alkenylphenols with an aldehyde such as formaldehyde are generally recovered as viscous liquids,

it is also possible to obtain hard resinous materials by condensing equimolar quantities of alkenylphenols and aldehyde in the presence of an alkaline catalyst and then acidifying the reaction mixture to a pH of about 2.0. The resulting hard materials are especially useful as varnish resins.

The acid catalyzed condensation reaction is best carried out by first admixing the formaldehyde, or formaldehyde producing substance, with the mixture of alkenylphenols and the acidic catalyst. The resulting mixture is then heated to a temperature of about 50 C. to 150 C. for about 2 to 3 hours, after which the water present in the reaction mixture is stripped off by distillation at reduced pressure, leaving the desired resin as a hard, grindable material. The reaction can, however, also be carried out simply by admixing the reactants and the acidic catalyst and allowing the mixture to stand at room temperature for 48 hours, or by maintaining the reaction mixture at temperatures even higher than 150 C.

As indicated hereinabove, either the acid or alkaline catalyzed condensation product of 'a mixture of alkenylphenols and an aldehyde, or the condensation product obtained in the absence of any catalyst, may be utilized in the preparation of the varnish compositions of this invention. In preparing the varnish compositions, the resin prepared in the methods described above is first heated with a drying oil or a semi-drying oil. For convenience, the term drying oil, wherever used hereinafter, is intended to include semi-drying oils. Such oils include linseed oil, soybean oil, castor oil, wood oil or tung oil, oiticica oil, perilla oil, sardine oil, menhaden oil and the like. One preferred method of formulating the varnish composition consists in placing the entire amount of resin and about half of the charge of the drying oil into a reactor equipped with stirrer and heating means. The resulting mixture is then heated to about 230 C. to 240 C. under an atmosphere of an inert gas such as nitrogen or carbon dioxide and this temperature is maintained until a resin string of about 15 to 20 inches can be pulled from a cooled drop on a glass surface. At this point the remaining quantity of oil is added and the reaction mixture again held at the desired temperature until a 20 to 30 inch string is obtained. The completed reaction product is then poured into an equal amount of a solvent such as an aromatic or aliphatic naphtha, toluene, xylene or the like, to form the final varnish composition. Alternatively, all of the reactants can initiailly be charged into the reactor and heated to a temperature of about 300 C. under an inert atmosphere until a 25 to 30 inch string is obtained and the completed reaction product then poured into an accordance with the present invention. The examples are not, however, intended to limit the invention, inasmuch as there are, of course, numerous possible variations and modifications.

. Example I One hundred forty-eight parts of a mixture of monobutenylphenols (oand p-monobutenylphenols) and 10 parts of sodium hydroxide in parts of water were mixed under a nitrogen atmosphere with uflicient cooling to keep the temperature below about 35 C. When a homogeneous solution was obtained, 163 parts of 37 percent formalin, methanolfree, containing60 grams (2 moles) of solid formaldehyde, were added at a moderate rate and cooling was continued to keep the temperature below about 35 C. Stirring was'continued for about 48 hours at room temperature. At the end of this time the reaction mixture was acidified to a pH of 5.0 with a mixture of concentrated hydrochloric acid and water (50 percent acid and 50 percent water) and the resulting water-insoluble layer of the resin was washed 4 times with lukewarm water. The resin was then dehydrated by vacuum stripping at steam temperatures under 20 mm. to 50 mm. pressure. The yield based on the quantity of alkenylphenols utilized was percent, the viscosity at 25 C. was W to Z (Gardner), and the resulting resin was completely miscible with ethanol, butanol, toluene and Xylene.

Example 11 Example I was repeated using each of the following formaldehyde:butenylphenol ratios: 0821, 1:1, 2:1, and 4:1. In each run a resin was obtained which gave light colored, fast curing films and which was compatible with drying oils, varnishes, alkyd resins and a great many other film forming materials.

Example III Several different aldehydes were condensed with mixed butenylphen'ols, including mono, diand tributenylphenols. The aldehyde utilized, the catalyst concentration, the mole ratio of aldehyde to butenylphenol, the reaction time and temperature (degrees centigrade) are set forth in the following table:

Example IV The following materials were charged into a glass lined reactor:

24.6 pounds mixed butenylphenols (monobutenylphenols,

diand tributenylphenols) 27.0 pounds formalin solution (37 percent formaldehyde) 1.7 pounds sodium hydroxide 1.7 pounds water 0.12 pound sodium hydrosulfite The resulting mixture was cooled to 75 F. to 80 F. and the reaction mixture agitated for 5 hours after which it was allowed to stand for 43 hours. The reaction mixture was then acidified to a pH of 5.0 with 68' percent sulfuric acid, and'allowed to stand until a water layer settled out. The water layer was .then drawn offend.

discarded. To the wet resin (36.25 pounds) 0.04 pound of an aminotetracarboxylic acid. known commercially as Sequestrene AA was added. The resin was then heated to 220 F. and stripped with an inert gas (nitrogen) until a Gardner viscosity of W at 75 percent solids in n-butanol was reached. The resin was then thinned with 10 pounds of n-butanol and filtered at 110 F. The following is the analysis of the final material:

Weight per gallon 8.45 pounds. Solids 66.2 percent at ll C. Viscosity Q to R (Gardner).

The resin thus prepared was roller coated on tin plate and cured at 350 F. for 20 minutes. The resulting film was of a thickness such that the film weighed 16 mgm./4 sq. in., and was light colored, mar-resistant and insoluble in acetone.

Example V One hundred sixty two grams (1 mole) of a mixture of pentenylphenols was placed in a glass lined reactor fitted with a condenser. Sixty-four and eight-tenths grams of formalin solution (0.8 mole formaldehyde) were then added to the pentenylphenols at a temperature of 24 C. Five cc. of concentrated hydrochloric acid were added except that the resin utilized in each example was prepared by the acidic condensation of a mixture of butenylphenols with formaldehyde according to the method described in the examples. In each example, the resin and oil were cooked together ata temperature of about 230 C. to 240 C. until ato 30-inch string was obtained afterwhich the resulting reaction mixture was addedto an. equal quantity of a high flash naphtha solvent. Also, in each example, the oil utilized was linseed oil. The

Films prepared from the varnish compositions of Examples XIII, XIV, and XV, in addition to possessing the properties listed in the foregoing table, are of a very light straw color, and. in this characteristic difIer subz y 'Q the PP tbe tempel'atufe rising stantially from varnishes in which the resinous com- 28 dm'lng the addltlon 3 the acld- The reaiftlon ponent is the condensation product of crotylphenol with P was then heate d at 95 hours: dlmng whlch an aldehyde such as formaldehyde, the latter varnish Elctloll mlxtufe Was CQBUDUOUSIY agltated- The composition being of an extremely dark, reddish color. reaction mixture was then distilled at reduced pressures until all of the water was removed, the percent solids at 30 flxample XVI Pomt bemg 76 Percent 100 P Sample of The bodying time required to obtain a useful varnish resm was heatfid blown Wlth m? gas at 175 from a butenylphenol-formaldehyde resin was compared C. The resulting resin was hard and brittle. A second with the bodying time required to produce a useful vap 1 was baked at 175 for 11/2 hOurS- 9 35 nish from a p-tertiary butylphenol-formaldehyde resin mg t sample was Very The ,total weight of msm by preparing a varnish from each resin according to the obtained from the condensation reaction was 152.0 grams. following formulation:

Example V1 50 grams phenolic resin Example V was repeated except that 1 mole of a mix- 97 grams linseed 011 i i ig fig g i gg gi zsg i gz a; One-half of the linseed Oll and all of the p-tert1ary-- u e 0 S n p butylphenolic resin were admixed and heated for about dred fifty-nine and two-tenths grams of a gum-like resin a h L 25 mlnutes at 230 C., after which the remainder of aving 95.6 percent solids were obtained. On heating at 1750 C for 11/2 hows a Vet hard rindable resin was the linseed 011 was added. Heating was then continued btai 1 y g at a temperature of 230 C. to 235 C. until a per cent 0 n6 1, l V t E I XH solids of 53.3, a Gardner viscosity of B and a Gardner e 0 mmp e colorof 14 were attained. .This heating required 420 A Series Of "amish Compositifims Was P p utiliZ- minutes. The resinous material was then thinned with ing as the resinous component thereof resinous condensa- 113 grams f naphtha a d 7 grams of drier added, tion products of a mixture of alkenylphenols and alde- On -half of the linseed oil and all of the butenylhydes P p according to the methcds of ple phenol-formaldehyde resin were admixed and heated to The varnish formulations were prepared by heating onea temperature of 220 C., approximately 10 minutes half of the oil with the entire amount of resin until a 15 being required to reach this temperature. The remainder to 20 inch string was obtained from a cooled drop on a of the linseed oil was then added and heating continued glass surface and then adding the remainder of the oil at a temperature of 210 C. to 240 C. until a per cent and continuing the heating until a 20 to 30 inch string is solids of 55.7, a Gardner viscosity of E-F and a Gardner again obtained. The resulting reaction mixture was then color of 14-15 were attained. This heating step required added to an equal weight of a high flash naphtha solvent only 40 minutes, demonstrating that varnishes prepared to form the final varnish composition. The oil utilized, from alkenylphenol-aldehyde resins and drying oils such the gallon oil length, the butenylphenol-formaldehyde 0 as linseed oil require only a fraction of the bodying time ratio, the reaction time and temperature, the percent required to obtain useful varnishes from other phenolic solids and the viscosity are set forth in the following table: resins.

Gallon Molar Ratio Reaction Reaction Percent Gardner Example Oil Component Oil Butenylphenol- Time Tempera- Solids Vis- Length Formaldehyde (Mins) ture( C.) cosity Linseed 25 211 40 230-240 55.7" E-F 25 1. 5: 1 280-200 53. 2 o 25. 1:1 65 230-240 51. 1 s 11 2:1 so 170 42.1 A d0 10 2:1 50 148 53.3 13-0 50% Tung, 50% 25 2:1 as 230 50. 3 D-E Linseed.

Example XIII to Example XV A series of varnishes was prepared substantially ac- Example XVII Vamishes of the foregoing example were spread as a cording to the methods of Examples VII through XII, thin film on a panel and the drying rate determined. The

varnish containing the butenylphenol-formaldehyde resin dried to the print free state in only 3 hours, whereas the varnish containing the p-tertiary-butylphenol-formaldehyde resin required 7.8 hours to dry to a print free state. Moreover, the mar-resistance of the varnish containing the butenylphenol-formaldehyde resin was substantially better than that of the varnish containing the p-tertiarybutylphenol-formaldehyde resin.

When the above examples are repeated substituting for the resinous condensation product of a mixture of butenyl-phenols and formaldehyde the resinous condensation products of other alkenylphenols with other aldehydes, good varnish compositions are again obtained. Also, when other drying or semi-drying oils selected from those disclosed hereinabove are substituted for the linseed or tung oil of the above examples, varnish compositions are obtained which are in all respects equivalent to those of the specific examples.

From the foregoing description of the invention and the specific examples, it will be seen that the varnish compositions of the present invention constitute a novel and useful class of coating compositions. It is apparent, therefore, that various embodiments of the invention, in addition to thosespecifically disclosed, may be provided without departing from the spirit and scope of the invention as defined in the appended claims.

We claim:

1. A light colored varnish composition consisting essentially of the product obtained by heatingtogether a drying oil and the resinous condensation product of formaldehyde and a mixture of butenylphenols containing about 55 percent to 85 percent by weight of orthoand paramonobutenylphenols, and about 15 percent to percent by weight of diand tributenylphenols.

2. A light colored varnish composition consisting essentially of the product obtained by heating together a drying oil and the alkaline catalyzed resinous condensation product of formaldehyde and a mixture of butenylphenols containing about percent to percent by weight of orthoand para-monobutenylphenols, and about 15 percent to 45 percent by weight of diand tributenylphenols.

3. The varnish of claim 2 wherein the drying oil is linseed oil.

4. The varnish of claim 2 wherein the drying oil is References Cited in the file of this patent UNITED STATES PATENTS 2,006,043 Dykstra June 25, 1935 2,175,393 Hentrich et al Oct. 10, 1939 2,587,578 Jones Mar. 4, 1952 

1. A LIGHT COLORED VARNISH COMPOSITION CONSISTING ESSENTIALLY OF THE PRODUCT OBTAINED BY HEATING TOGETHER A DRYING OIL AND THE RESINIOUS CONDENSATION PRODUCT OF FORMALDEGYDE AND A MIXTURE OF BUTENYLPHENOLS CONTAINING ABOUT 55 PERCENT TO 85 PERCENT BY WEIGHT OF ORTHO- AND PARAMONOBUTTENYLPHENOLS, AND ABOUT 15 PERCENT TO 45 PERCENT BY WEIGHT OF DI- AND TRIBUTENYLPHENOLS. 